KR102514720B1 - Supported metallocene catalyst, method for preparing the same, and method for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a supported metallocene catalyst, a method for preparing the same, and a method for producing polyolefin using the same, and includes a support in which a compound containing boron is fixed through chemical bonding; A cocatalyst containing aluminum; and a supported metallocene catalyst characterized by supporting a metallocene compound, a method for preparing the same, and a method for producing polyolefin using the same are provided.

Description

Supported metallocene catalyst, method for preparing the same, and method for producing polyolefin using the same {SUPPORTED METALLOCENE CATALYST, METHOD FOR PREPARING THE SAME, AND METHOD FOR PREPARING POLYOLEFIN USING THE SAME}

The present invention relates to a supported metallocene catalyst for preparing polyolefin, and more particularly, to a high-performance supported metallocene catalyst, a method for preparing the same, and a method for preparing polyolefin using the same.

Since the metallocene catalyst has a uniform active site, the resulting polymer has a narrow molecular weight distribution, easy copolymerization, and uniform comonomer distribution. In addition, molecular weight, stereoregularity, crystallinity, and comonomer reactivity can be controlled according to the structure of the catalyst and the ligand. In the case of propylene polymerization, there is an advantage that the three-dimensional structure of the polymer can be controlled according to the symmetry of the catalyst. In particular, the existing Ziegler-Natta catalyst can produce only isotactic polypropylene, but when a metallocene catalyst is used, isotactic, syndiotactic, atactic as well as hemi-isotactic (hemiisotactic), etc., can be produced stereoregularly.

However, in the olefin polymerization technology using such a homogeneous metallocene catalyst, it is difficult to maintain the shape of the polymer in a gas phase process or slurry process, and an excessive amount of methylaluminoxane (MAO) must be used to exhibit the maximum activity of the metallocene catalyst. There is a problem. In order to solve this problem, it is necessary to use a metallocene catalyst supported on a suitable carrier. When the catalyst is supported in this way, the shape of the polymer produced can be controlled and the apparent density of the obtained polymer can be improved. It has the advantage of reducing the fouling phenomenon.

In general, a method for preparing a supported metallocene catalyst is a method in which a metallocene compound is physically and chemically bonded to a carrier and then contacted with methylaluminoxane, and a method in which methylaluminoxane is supported on a carrier and then A reaction method and a method in which a metallocene compound and methylaluminoxane are first contacted and then supported on a carrier are known. However, methylaluminoxane used for activation of the supported catalyst is expensive and requires an excessive amount compared to the metallocene catalyst, which accounts for a significant portion of the catalyst cost, which is a major factor in reducing the price competitiveness of metallocene-manufactured polyolefins in commercial terms. .

Therefore, efforts are being made to reduce the amount of aluminoxane such as the commonly used methylaluminoxane or replace it with other cocatalysts.

For example, a method of efficiently introducing a functional group into a tetraaryl boron anion (Patent Document 1), a method of using a cocatalyst for electron stabilization of non-coordinating anions for an intrinsically active cationic metallocene polymerization catalyst (Patent Document 2 ), etc.

However, in most of the prior art, when methylaluminoxane used for activation of the supported catalyst is changed and used, the catalytic activity is very poor, so a method for preparing a supported metallocene catalyst is required.

In addition, in order for such a supported metallocene catalyst to have the same high activity and copolymerizability as a homogeneous catalyst, a single active site catalyst structure must be maintained even after being supported, and to prevent reactor fouling, the catalyst must not be separated from the carrier during polymerization. . The particle size, particle size distribution and apparent density of the polymer depend on the particle shape and mechanical properties of the supported catalyst. However, polymers often accumulate on the walls of the reactor or form agglomerates during the polymerization process. This fouling can reduce the heat exchange efficiency between the reactor and the refrigerant, and cause serious problems during the polymerization process due to loss of reactor control due to overheating or formation of ropes and lumps.

Patent Document 1: JP 2003-183290 Patent Document 2: US 5,198,401

In order to solve this problem, the present invention prepares a supported metallocene catalyst by supporting a metallocene compound after supporting a cocatalyst containing aluminum on a carrier to which a compound containing boron is chemically bonded. The supported metallocene catalyst prepared in this way has significantly higher catalytic activity than the supported metallocene catalyst prepared using conventional methylaluminoxane, and has an effect of preventing fouling when applied to a slurry or gas phase process.

The present invention,

carrier;

(1) chemically combining a compound containing boron represented by Formula 1 or 2;

(2) supporting a cocatalyst containing aluminum on a carrier to which the compound containing boron is bonded; and

Step (3) of supporting one or more metallocene compounds represented by Chemical Formula 3 or 4 in step (2);

Method for producing a supported metallocene catalyst comprising a.

(However, the above steps (2) and (3) can be done at once or the order can be changed.)

[Formula 1]

[Formula 2]

(In Formulas 1 and 2,

B is a boron atom;

R is phenyl or phenyloxy, and phenyl or phenyloxy is 3 to 5 selected from fluorine, C1 to C20 alkyl optionally substituted by fluorine, or C1 to C20 alkoxy optionally substituted by fluorine. may be further substituted with two substituents;

[L ^a ] ⁺ is a C5 to C7 cycloalkyl radical, a (C1 to C20)alkyl(C6 to C20)aryl radical, or a (C6 to C30)aryl(C1 to C20)alkyl radical;

[L ^b -H] ⁺ is an ammonium or phosphonium ion substituted with 1 to 3 (C1 to C20) alkyl groups.)

[Formula 3]

[Formula 4]

(In Chemical Formulas 3 and 4,

M is a Group 4 transition metal;

Cp ¹ and Cp ² are each independently a ligand having a cyclopentadienyl skeleton;

The ligand is an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a silylalkyl group, a haloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. It may have 20 aryl groups, arylalkyl groups, alkylaryl groups, arylsilyl groups, silylaryl groups or halogen groups as substituents, and the substituents A ring can be formed by binding between the liver;

X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group group, an alkylaryl group, an arylsilyl group, a silylaryl group, an alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group, an aryloxy having 6 to 20 carbon atoms ( Aryloxy group, halogen group or amine group;

Q is an alkyl radical of 1 to 5 carbon atoms or a hydrocarbyl radical containing silicon, germanium, nitrogen, phosphorus, boron or aluminum;

R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl ( It is an arylalkyl group, an alkylaryl group, an arylsilyl group, or a silylaryl group.)

The present invention provides a method for producing a polyolefin, characterized in that polymerizing an olefinic monomer in the presence of the supported metallocene catalyst.

The supported metallocene catalyst of the present invention is prepared by supporting a cocatalyst containing aluminum on a carrier to which a compound containing boron is chemically bonded, and then supporting the metallocene compound thereon. The supported metallocene catalyst prepared as described above has a remarkably high catalytic activity compared to the conventional supported metallocene catalyst supporting methylaluminoxane. In addition, the polyolefin production method of the present invention using the supported metallocene catalyst prepared according to the present invention can be applied to a polyolefin polymerization process that is polymerized at low or high pressure, and has an effect of preventing reactor fouling.

Hereinafter, a supported metallocene catalyst according to a specific embodiment of the present invention, a method for preparing the same, and a method for preparing polyolefin using the same will be described.

In order to achieve the above technical problem, the present invention

carrier;

(1) chemically combining a compound containing boron represented by Formula 1 or 2;

(2) supporting a cocatalyst containing aluminum on a carrier to which the compound containing boron is bonded; and

Step (3) of supporting one or more metallocene compounds represented by Formula 3 or 4 in Step (2);

Method for producing a supported metallocene catalyst comprising a.

(However, the above steps (2) and (3) can be done at once or the order can be changed.)

[Formula 1]

[Formula 2]

(In Formulas 1 and 2,

B is a boron atom;

R is phenyl or phenyloxy, and phenyl or phenyloxy is 3 to 5 selected from fluorine atom, C1 to C20 alkyl optionally substituted by fluorine atom, or C1 to C20 alkoxy optionally substituted by fluorine atom. may be further substituted with substituents;

[L ^a ] ⁺ is a C5 to C7 cycloalkyl radical, a (C1 to C20)alkyl(C6 to C20)aryl radical, or a (C6 to C30)aryl(C1 to C20)alkyl radical;

[L ^b -H] ⁺ is an ammonium or phosphonium ion substituted with 1 to 3 (C1 to C20) alkyl groups.)

[Formula 3]

[Formula 4]

(In Chemical Formulas 3 and 4,

M is a Group 4 transition metal;

Cp ¹ and Cp ² are each independently a ligand having a cyclopentadienyl skeleton;

The ligand is an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a silylalkyl group, a haloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. It may have 20 aryl groups, arylalkyl groups, alkylaryl groups, arylsilyl groups, silylaryl groups or halogen groups as substituents, and the substituents A ring can be formed by binding between the liver;

X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group group, an alkylaryl group, an arylsilyl group, a silylaryl group, an alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group, an aryloxy having 6 to 20 carbon atoms ( Aryloxy group, halogen group or amine group;

Q is an alkyl radical of 1 to 5 carbon atoms or a hydrocarbyl radical containing silicon, germanium, nitrogen, phosphorus, boron or aluminum;

R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl ( It is an arylalkyl group, an alkylaryl group, an arylsilyl group, or a silylaryl group.)

According to a preferred embodiment of the present invention, the carrier used in the present invention is a porous solid particulate made of silica, silica-alumina or silica-magnesia, preferably an inorganic material such as silicon and / or aluminum oxide, Most preferably, it is silica which is present in the form of spherical particles, for example, particles obtained by a spray drying method, and has an OH group or other functional group containing an active hydrogen atom. The carrier has micropores with an average particle size of 10 to 250 microns, preferably 10 to 150 microns, an average diameter of 50 to 500 Å, and a micropore volume of 0.1 to 10 ml/g, preferably 0.5 to 5 ml. /g. The surface area of the carrier is 5 to 1000 m 2 /g, preferably 50 to 600 m 2 /g.

When silica is used as the carrier, it should have at least some active hydroxyl groups, and the hydroxyl group concentration is preferably 0.5 to 2.5 mmol or more, more preferably 0.7 to 1.6 mmol/g per 1 g of the silica, and 0.5 If it is less than 2.5 mmol, the amount of methylaluminoxane supported decreases and activity is lowered, which is undesirable, and if it exceeds 2.5 mmol, the catalyst component is deactivated by OH, which is not preferable.

In the organometallic compound represented by Formula 1 or 2 containing boron bound to a carrier, B is a boron atom, R is phenyl or phenyloxy, and phenyl or phenyloxy is a fluorine atom, substituted or unsubstituted by a fluorine atom It may be further substituted with 3 to 5 substituents selected from C1 to C20 alkyl, or C1 to C20 alkoxy optionally substituted by a fluorine atom. [L ^a ] ⁺ is a C5 to C7 cycloalkyl radical, a (C1 to C20)alkyl(C6 to C20)aryl radical, or a (C6 to C30)aryl(C1 to C20)alkyl radical, [L ^b -H] ⁺ is an ammonium or phosphonium ion substituted with 1 to 3 (C1 to C20) alkyl groups.

Specific examples of the boron compound included in the above formula are trimethylammonium tri(phenyl) boron, triethylammonium tri(phenyl) boron, tripropylammonium tri(phenyl) boron, tributylammonium tri(phenyl) boron, and trimethylammonium. Tri(p-tolyl) boron, trimethylammoniumtri(o,p-dimethylphenyl)boron, trimethylammoniumtri(p-trifluoromethylphenyl)boron, tributylammoniumtri(pentafluorophenyl)boron,N,N- Dimethylamilidium tri(phenyl) boron, N,N-diethylamidium tri(phenyl) boron, N,N-dimethylamidium tri(pentafluorophenyl)boron, N,N-diethyla Millidium tri(pentafluorophenyl) boron, trimethylphosphonium tri(phenyl) boron, tripethylphosphonium tri(phenyl) boron, trimethylphosphonium tri(pentafluorophenyl)boron, tripethylphosphonium tri( pentafluorophenyl) boron, triphenylcarbonium tri(p-trifluoromethylphenyl) boron, triphenylcarbonium tri(pentatrifluorophenyl)boron, or trityltri(pentatrifluorophenyl)boron lophenyl) boron and the like may be included.

Meanwhile, the molar ratio of [boron]/[transition metal] in the supported metallocene catalyst may be 0.01 to 1,000, preferably 0.1 to 100, and more preferably 0.2 to 10, when the molar ratio is less than 0.01. Since the content of boron is too small, the effect of increasing the catalytic activity is very low, and when it exceeds 1,000, the activity does not increase any more, and the content of the borate compound remaining unsupported increases, causing fouling in the reactor during polymerization. .

In the catalyst manufacturing and supporting process, preferably, after an organometallic compound containing boron is bonded to a carrier, a cocatalyst containing aluminum is supported. At this time, when silica is used as the carrier, the hydroxy group of silica is Under anhydrous conditions, it reacts with the aluminum-based cocatalyst to support the aluminum-based cocatalyst to provide a location for the metallocene to be supported, and at the same time to protect the metallocene, which reacts very sensitively to external catalyst poisons and easily loses its activity. play a role Therefore, the higher the supported amount of the aluminum-based cocatalyst, the higher the supported amount of metallocene, and the higher the probability of not being poisoned by external catalyst poisons, thereby increasing the activity.

The carrier treated with the organometallic compound containing boron thus dried may be mixed with the following cocatalyst to form a carrier supported with the cocatalyst. The cocatalyst is an organometallic compound containing aluminum, and is generally the same as the cocatalyst used when polymerizing olefins in the presence of a metallocene catalyst. When such a cocatalyst is supported, a bond is created between the hydroxy group in the support and the aluminum metal.

Cocatalysts include aluminoxanes or organoaluminums. The aluminoxane includes straight-chain and/or cyclic alkylaluminoxane oligomers, and when the aluminoxane is a straight-chain aluminoxane oligomer, it is represented by the formula R-(Al(R)-O)n-AlR ₂ and is a cyclic aluminoxane. In the case of oxane oligomers, it is represented by the formula (-Al(R)-O-)m, where R is a C1 to C8 alkyl group, preferably methyl, n is 1 to 40, preferably 10 to 20, , m is 3 to 40, preferably 3 to 20.

The aluminoxane is a mixture of oligomers with a very wide molecular weight distribution, and usually has an average molecular weight of about 800 to 1200, and is mainly maintained as a solution in toluene. As a specific example, 10% or 30 % of methylaluminoxane and the like. As the above organic aluminum compound, an alkyl aluminum compound represented by the general formula AlRnX(3-n) (where R is an alkyl group having 1 to 16 carbon atoms, X is a halogen element, and 1≤n≤3) can be used Specific examples of the alkyl aluminum compound include, preferably, triethyl aluminum, trimethyl aluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, and tri2-methylpentyl. Aluminum or the like is used, and triisobutylaluminum, triethylaluminum, trinormalhexylaluminum or trinormaloctylaluminum is particularly preferably used.

In the metallocene compound represented by Formula 3 or 4, M may be selected from elements of groups 3 to 10 on the periodic table, preferably from group 4 elements.

In addition, Cp ¹ and Cp ² are each independently a ligand having a cyclopentadienyl skeleton, for example, a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, or a flue and the like, and the ligand includes an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a silylalkyl group, a haloalkyl group, and a carbon atom having 3 to 20 carbon atoms. A cycloalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group, an alkylaryl group, an arylsilyl group, a silylaryl group, or a halogen It may have a group as a substituent, and a ring may be formed by bonding between the substituents.

In addition, X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group ) group, an alkylaryl group, an arylsilyl group, a silylaryl group, an alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group, an aryloxy group having 6 to 20 carbon atoms (Aryloxy) group, halogen group or amine group.

In addition, Q is a component that connects ligands Cp ¹ and Cp ² without directly coordinating to the transition metal M, and is an alkyl radical having 1 to 5 carbon atoms or a hydrocarbyl radical containing silicon, germanium, nitrogen, phosphorus, boron, or aluminum.

In addition, R is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl (Arylalkyl) group, alkylaryl group, arylsilyl group or silylaryl group.

The compound represented by Formula 3 is, for example, bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, bis( Ethylcyclopentadienyl)zirconium dichloride, bis(iso-propylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(iso-butylcyclopentadienyl)zirconium di Chloride, bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(2-methylindenyl) Cyclopentadienyl selected from the group comprising zirconium dichloride, bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride and bis(n-butylcyclopentadienyl)hafnium dichloride It may be a metallocene compound without a ligand connecting rings.

In addition, the compound represented by Formula 4 is, for example, rac-ethylenebis (1-indenyl) zirconium dichloride, rac-ethylenebis (1-indenyl) hafnium dichloride, rac-ethylenebis (1-tetrahydro-indenyl ) zirconium dichloride, rac-ethylenebis(1-tetrahydro-indenyl)hafnium dichloride, rac-dimethylsilanediylbis(2-methyl-tetrahydrobenzindenyl)zirconium dichloride, rac-dimethylsilanediyl Bis(2-methyl-tetrahydrobenzindenyl)hafnium dichloride, rac-diphenylsilanediylbis(2-methyl-tetrahydrobenzindenyl)zirconium dichloride, rac-diphenylsilanediylbis(2- Methyl-tetrahydrobenzindenyl) hafnium dichloride, rac-dimethylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl-4, 5-benzindenyl) hafnium dichloride, rac-diphenylsilanediylbis (2-methyl-4,5-benzindenyl) zirconium dichloride, rac-diphenylsilanediylbis (2-methyl-4, 5-benzindenyl) hafnium dichloride, rac-dimethylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-dimethylsilanediylbis (2-methyl-5 ,6-cyclopentadienylindenyl) hafnium dichloride, rac-diphenylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) zirconium dichloride, rac-diphenylsilanediylbis (2-methyl-5,6-cyclopentadienylindenyl) hafnium dichloride, id, rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylbis (2 -Methyl-4-phenylindenyl) hafnium dichloride, rac-diphenylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-diphenylsilylbis (2-methyl-4-phenylindenyl) ) hafnium dichloride, iso-propylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenylmethyl Iidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) hafnium dichloride Chloride, iso-propylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, iso-propylidene (3-methylcyclopentadienyl) (9-fluorenyl) hafnium dichloride, Diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (3-methylcyclopentadienyl) (9-fluorenyl) hafnium dichloride, diphenyl Silyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (2 ,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, Diphenylmethylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (3-tert-butylcyclopentadienyl ) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert- Butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium di Chloride, 1,2-ethylenebis(9-fluorenyl)zirconium dichloride, 1,2-ethylenebis(9-fluorenyl)hafnium dichloride, rac-[1,2-bis(9-fluorenyl) )-1-phenyl-ethane]zirconium dichloride, rac-[1,2-bis(9-fluorenyl)-1-phenyl-ethane]hafnium dichloride, [1-(9-fluorenyl)-2 -(5,6-Cyclopenta-2-methyl-1-indenyl)-ethane]zirconium dichloride, [1-(9-fluorenyl)-2-(5,6-cyclopenta-2-methyl- 1-indenyl)-ethane] hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-phenyl-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl) -4,6,6-trimethyl-2-phenyl-tetrahydropentalene] hafnium dichloride, iso-propylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride Rolide, iso-propylidene(2-phenyl-cyclopentadienyl)(9-fluorenyl)hafnium dichloride, diphenylmethylidene(2-phenyl-cyclopentadienyl)(9-fluorenyl)zirconium Dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (9-fluorenyl) hafnium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert- Butylfluoren-9-yl) zirconium dichloride, isopropylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) zirconium dichloride, diphenylmethylidene (2-phenyl-cyclopentadienyl) (2,7- Di-tert-butylfluoren-9-yl) hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (p-tolyl) -tetrahydropentalene] zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(p-tolyl)-tetrahydropentalene]hafnium dichloride, [isopropylidene-(2-(p-tolyl)-cyclopenta Dienyl)-(9-fluorenyl)]zirconium dichloride, [isopropylidene-(2-(p-tolyl)-cyclopentadienyl)-(9-fluorenyl)]hafnium dichloride, [4 -(fluorenyl)-4,6,6-trimethyl-2-(m-tolyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2 -(m-tolyl)-tetrahydropentalene]hafnium dichloride, [isopropylidene(2-(m-tolyl)-cyclopentadienyl)-(9-fluorenyl)]zirconium dichloride, [isopropyl Iidene(2-(m-tolyl)-cyclopentadienyl)-(9-fluorenyl)]hafnium dichloride, [diphenylmethylidene(2-(m-tolyl)-cyclopentadienyl)-(9 -fluorenyl)] zirconium dichloride, [diphenylmethylidene (2- (m-tolyl) -cyclopentadienyl) - (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- ( m-tolyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]zirconium dichloride, [isopropylidene(2-(m-tolyl)-cyclopentadienyl) (2,7-di-tert-butyl flu Oren-9-yl)] hafnium dichloride, [diphenylmethylidene (2-(m-tolyl)-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride Chloride, [diphenylmethylidene(2-(m-tolyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]hafnium dichloride, [4-(fluorenyl) )-4,6,6-trimethyl-2-(o-tolyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(o-tolyl) ) -Tetrahydropentalene] hafnium dichloride, [isopropylidene (2- (o-tolyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [isopropylidene (2- (o -Tolyl)-cyclopentadienyl)(9-fluorenyl)]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(2,3-dimethylphenyl)-tetra hydropentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,3-dimethylphenyl) -tetrahydropentalene] hafnium dichloride, [4- (fluenyl) Orenyl) -4,6,6-trimethyl-2- (2,4-dimethylphenyl) -tetrahydropentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2 -(2,4-dimethylphenyl)-tetrahydropentalene]zirconium dichloride, [isopropylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]zirconium dichloride Chloride, [isopropylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]hafnium dichloride, [isopropylidene(2-(2,4-dimethylphenyl) -Cyclopentadienyl)(9-fluorenyl)]zirconium dichloride, [isopropylidene(2-(2,3-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]hafnium dichloride , [diphenylmethylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl)] zirconium dichloride, [diphenylmethylidene (2- (2,3-dimethylphenyl) )-cyclopentadienyl)(9-fluorenyl)]hafnium dichloride, [diphenylmethylidene(2-(2,4-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)]zirconium Dichloride, [diphenylmethylidene(2-(2,4-dimethine) Tylphenyl) -cyclopentadienyl) (9-fluorenyl)] hafnium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert -Butylfluoren-9-yl)] zirconium dichloride, [isopropylidene (2- (2,3-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluorene-9- yl)] hafnium dichloride, [isopropylidene(2-(2,4-dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]zirconium dichloride, [Isopropylidene (2- (2,4-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2 -(2,3-dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)]zirconium dichloride, [diphenylmethylidene(2-(2,3- Dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [diphenylmethylidene (2- (2,4-dimethylphenyl) -cyclopenta dienyl) (2,7-di-tert-butylfluoren-9-yl)] zirconium dichloride, [diphenylmethylidene (2- (2,4-dimethyl phenyl) -cyclopentadienyl) (2, 7-di-tert-butylfluoren-9-yl)] hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(2,6-dimethylphenyl)-tetrahydropenta Ren] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (2,6-dimethylphenyl) -tetrahydropentalene] hafnium dichloride, [4- (fluorenyl )-4,6,6-trimethyl-2-(3,5-dimethylphenyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-( 3,5-dimethylphenyl)-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentalene]zirconium dichloride, [4 -(Fluorenyl)-4,6,6-trimethyl-2-tetramethylphenyl-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(2 ,4-dimethoxyphenyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4 ,6,6-trimethyl-2-(2,4-dimethoxyphenyl)-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3, 5-dimethoxyphenyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3,5-dimethoxyphenyl)-tetrahydropentalene] Hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(chlorophenyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6, 6-Trimethyl-2-(chlorophenyl)-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(fluorophenyl)-tetrahydropentalene] Zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(fluorophenyl)-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6 ,6-trimethyl-2-(difluorophenyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(difluorophenyl)-tetra Hydropentalene] hafnium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (pentafluorophenyl) -tetrahydropentalene] zirconium dichloride, [4- (fluorene Nyl)-4,6,6-trimethyl-2-(difluorophenyl)-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(tert -Butyl-phenyl)-tetrahydropentalene] hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3,5-trifluoromethyl-phenyl)-tetrahydropenta Ren] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2- (3,5-trifluoromethyl-phenyl) -tetrahydropentalene] hafnium dichloride, [4- (fluorenyl)-4,6,6-trimethyl-2-(3,5-di-tert-butylphenyl)tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6, 6-Trimethyl-2-(3,5-di-tert-butylphenyl)tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(biphenyl) -Tetrahydropentalene] zirconium dichloride, [4-(fluorene Nyl)-4,6,6-trimethyl-2-(biphenyl)-tetrahydropentalene]hafnium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-naphthyl-tetra hydropentalene] zirconium dichloride, [4- (fluorenyl) -4,6,6-trimethyl-2-naphthyl-tetrahydropentalene] hafnium dichloride, [4- (fluorenyl) -4, 6,6-Trimethyl-2-(3,5-diphenyl-phenyl)-tetrahydropentalene]zirconium dichloride, [4-(fluorenyl)-4,6,6-trimethyl-2-(3, 5-diphenyl-phenyl)-tetrahydropentalene] hafnium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-(2 ,6-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(2-(3,5-dimethylphenyl)-cyclopentadienyl)(9-fluorenyl) Zirconium dichloride, isopropylidene(2-(2,4-dimethoxyphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(2-(3,5-dimethoxyphenyl) )-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(2-(2,3-dimethoxyphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, Isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (chlorophenyl) -cyclopentadienyl) (9 -fluorenyl) zirconium dichloride, isopropylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopenta Dienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (di Fluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (pentafluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (9-fluoro Renyl) zirconium dichloride, isopropylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (3,5-di-tert- Butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2- (biphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-(3,5-diphenyl-phenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(2-naphthyl-cyclopentadienyl)(9-fluorenyl) ) Zirconium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,6-dimethylphenyl) -cyclopentadiene Nyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (3,5-dimethylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene ( 2-(2,4-dimethoxyphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene(2-(3,5-dimethoxyphenyl)-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2 -(2,6-dimethoxyphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene(2-(chlorophenyl)-cyclopentadienyl)(9-fluorenyl) ) Zirconium dichloride, diphenylmethylidene (2- (dichlorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (trichlorophenyl) -cyclopentadienyl ) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (di Fluorophenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene(2-(pentafluorophenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride , Diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl ) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2- (tert-butylphenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-( 3,5-di-tert-butylphenyl)-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylidene(2-(biphenyl)-cyclopentadienyl)(9-fluorene Nyl) zirconium dichloride, diphenylmethylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylidene (2-naphthyl- Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride , isopropylidene (2- (2,6-dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3 ,5-dimethylphenyl)-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (2,4-dimethoxyphenyl) -cyclo Pentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7 -Di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-(2,3-dimethoxyphenyl)-cyclopentadienyl) (2,7-di-tert-butylfluorene -9-yl) hafnium dichloride, isopropylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride , Isopropylidene (2- (chlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (dichlorophenyl) -cyclo Pentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (trichlorophenyl) -cyclopentadienyl) (2,7-di-tert -Butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (fluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride , isopropylidene (2- (difluorophenyl) -Cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (pentafluoro phenyl) -cyclopentadienyl) (2,7- Di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (2,7-di-tert-butyl Fluoren-9-yl) hafnium dichloride, isopropylidene (2- (tert-butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, Isopropylidene (2- (3,5-di-tert-butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2 -(Biphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride, isopropylidene(2-(3,5-diphenyl-phenyl)-cyclo Pentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, isopropylidene (2-naphthyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) Oren-9-yl) hafnium dichloride, diphenylmethylidene (2-tetramethylphenyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-(2,6-dimethylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride, diphenylmethylidene(2-(3,5- Dimethylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,4-dimethoxyphenyl) -cyclopentadiene Nyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-dimethoxyphenyl) -cyclopentadienyl) (2,7- Di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (2,3-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluorene -9-yl) hafnium dichloride, diphenylmethylidene (2- (2,6-dimethoxyphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium di Chloride, diphenylmethylidene (2- (chlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) Hafnium dichloride, diphenylmethylidene (2- (dichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-( Trichlorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (fluorophenyl) -cyclopentadienyl) ( 2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (difluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluorenyl) Oren-9-yl) hafnium dichloride, diphenylmethylidene (2- (pentafluorophenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, Diphenylmethylidene (2- (3,5-trifluoromethyl-phenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2-(tert-butylphenyl)-cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dichloride, diphenylmethylidene(2-(3,5-di- Tert-butylphenyl) -cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (biphenyl) -cyclopentadienyl) ( 2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, diphenylmethylidene (2- (3,5-diphenyl-phenyl) -cyclopentadienyl) (2,7-di- tert-butylfluoren-9-yl) hafnium dichloride and diphenylmethylidene (2-naphthyl-cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dichloride, etc. It may be a metallocene compound having a ligand connecting cyclopentadienyl rings selected from the group containing.

On the other hand, the solvent used for washing in the above step of the supported catalyst preparation process is as follows. For the first washing step, aromatic hydrocarbon-based solvents such as benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene or toluene are suitable, and for the second washing step, pentane It is recommended to use an aliphatic hydrocarbon-based solvent such as pentane, hexane, heptane, octane, nonane, decane, undecane or dodecane. desirable.

The supported metallocene catalyst obtained according to the production method of the present invention can be used for polymerization of olefinic monomers. In the method for producing polyolefin, the polymerization reaction is carried out in the presence or absence of a hydrocarbon solvent at a temperature of preferably 60 to 120 ° C, more preferably 65 to 100 ° C, most preferably 70 to 80 ° C, and preferably 2 to 80 ° C. It is carried out at a pressure of 40 atmospheres, more preferably 10 to 30 atmospheres. If the polymerization temperature in the reactor is less than 60 ° C, sufficient polymerization efficiency cannot be obtained, and if it exceeds 100 ° C, there is a problem that polymer lumps are easily generated. In addition, if the operating pressure in the reactor is less than 2 atmospheres, sufficient polymerization efficiency cannot be obtained due to low ethylene partial pressure, and if it exceeds 40 atmospheres, the control of the reaction becomes difficult and unreasonable pressure is applied to the reactor.

The supported metallocene catalyst obtained according to the production method of the present invention is a main catalyst, and the supported metallocene catalyst component prepared above may be pre-polymerized with ethylene or α-olefin before being used as a component in a polymerization reaction. The pre-polymerization may be carried out in the presence of the catalyst component and an organoaluminum compound such as triisobutylaluminum at a sufficiently low temperature and ethylene or olefin monomer pressure in the presence of a hydrocarbon solvent such as hexane. Pre-polymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape. The polymer/catalyst weight ratio after prepolymerization is usually between 0.1:1 and 200:1. Preferred organometallic compounds are trialkylaluminum having an alkyl group of 1 to 6 carbon atoms, such as triethylaluminium or triisobutylaluminum, and mixtures thereof. Optionally, one or more halogen or hydride groups such as ethylaluminium dichloride, diethylaluminum chloride, ethylaluminium sesquichloride or diisobutylaluminum hydride may be used in the organoaluminum compound.

The product obtained by the polymerization method of the present invention is a solid high molecular weight polyolefin homopolymer or copolymer, and the yield of the polymer is sufficiently high that removal of catalyst residues is not required, and it has excellent bulk density and fluidity.

The olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene , 1-tetradecene, 1-hexadecene and 1-aitocene, and the dienes are straight-chain, branched-chain or cyclic hydrocarbon dienes having 6 to 15 carbon atoms. Suitable conjugated dienes include straight-chain acyclic dienes. dienes such as 1,4-hexadiene or 1,6-octadiene; branched chain acyclic dienes such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene or mixed isomers of dihydromyricene and dihydrooxinene; monocyclic acyclic dienes such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene or 1,5-cyclododecadiene; or multi-ring acyclic fused and bridged ring dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene; bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5- Vinyl-2-norbornene or norbornadiene is preferred.

The supported metallocene catalyst obtained according to the preparation method may be polymerized in the presence of appropriate additives. The above additives include cationic agents, anionic agents, nonionic agents, organometallic agents, polymers or mixtures thereof. Suitable examples of cationic agents may be selected from quaternary ammonium, sulfonium or phosphonium salts having a long hydrocarbon chain (preferably C5 to C20), such as chlorides, sulfates, nitrates, or their hydrogen phosphate salts. Examples of suitable nonionic agents include partial fatty acid esters of polyhydric alcohols; alkoxylated fatty alcohols such as ethoxylated or propoxylated fatty alcohols; polyethylene glycol (PEG) esters of fatty acids and alkylphenols; glyceryl esters of fatty acids and sorbitol esters; ethylene oxide adducts of fatty amines or fatty acid amides; ethylene oxide adducts of alkylphenols; ethylene oxide adducts of alkyl naphthols; polyethylene glycol, fatty acid esters of alkyldiethanolamines, or mixtures thereof. Examples of suitable organometallic agents may be selected from neoalkyl titanates and zirconates, or mixtures thereof. Examples of suitable polymerizers include polyethylene glycol hexadecyl ether; ethylene oxide/propylene oxide copolymer; or polyoxyalkylene compounds such as mixtures thereof.

An example of a suitable commercially available additive is the trademark Armostat ^® (e.g. Armostat ^® 300(N,N-bis-(2-hydroxyethyl)-(C.sub.10-C.sub) from Akzo Nobel Corporation. .20) additives for alkylamines), Armostat ^® 410 (bis(2-hydroxyethyl)cocoamine) and Armostat ^® 600 (N,N-bis(2-hydroxy-ethyl)alkylamine); additives under the trade designation Chemax X997 ^® (>50% of dicocoalkyl-dimethyl ammonium chloride, about 35% of 1-hexene, <2% of isopropanol and <1% of hexanes); additives under the trade designation Atmere 163 (N,N-bis(2-hydroxy-ethyl)alkylamine) from ICI Americas; additives under the trade name Statsafe 6000 (dodecylbenzenesulfonic acid) from Innospec Limited; Trade name ^Octastat® 3000 from Octel Performance Chemicals (about 40-50% toluene, about 0-5% propan-2-ol, about 5-15% DINNSA (dinonaphthasulfonic acid), about 15-30% of solvent naphtha, about 1 to 10% trade secret polymer containing N, and about 10 to 20% trade secret polymer containing S) additives; additives from BASF under the trade name Kerostate 8190 (about 10-20% alkenes (polymers with sulfur dioxide), about 3-8% benzenesulfonic acid (4-C10-13-sec-alkyl derivatives) and organic solvents); EI Du Pont de Nemours &amp; ^Co. (about 14 weight percent polybutene sulfate, about 3 weight percent aminoethanol epichlorohydrin polymer, about 13 weight percent alkylbenzenesulfonic acid, about 70 weight percent toluene and trace amounts of aliphatic alkyls and quaternary ammonium salts of propyl alcohol); Synperonic PEL121 from Uniqema (ethylene oxide-propylene oxide-ethylene oxide block copolymer, about 10% propylene oxide, MW about 4,400 Da); and the like. A preferred example of the additive is dodecylbenzenesulfonic acid or an ethylene oxide-propylene oxide block copolymer.

Preferred examples of additives for use in the present invention are Stadis 450, Statsafe 6000 and Synperonic PEL 121. Stadis 450 and Statsafe 6000 are preferably used for Ziegler-Natta catalysts. Synperonic PEL121 is particularly preferred for use with metallocene catalysts.

The present invention will be described in detail by the following Examples and Comparative Examples, but the present invention is not limited thereto.

Example

Organic reagents and solvents necessary for catalyst production and polymerization were used after being purified by standard methods from reagent suppliers, and high-purity ethylene was used after passing through a water and oxygen filter. The reproducibility of the experiment was improved by blocking contact between air and moisture in all stages of support and olefin polymerization.

Example 1

<Manufacture of Supported Catalyst>

2.5 g of calcined silica (Grace Davison, SYLOPOL 2402) was weighed into a 1L reactor maintained in a nitrogen state, and 10 ml of toluene was added as a slurry, followed by stirring. After sufficiently dispersing the silica, 0.4 g of Tri(pentafluorophenyl)borane and 0.35 ml of dimethylaniline dissolved in 20 ml of toluene were sequentially injected into the reactor.

Then, after stirring at 100° C. for 2 hours, the supernatant was removed at room temperature and washed with toluene. 2.5 ml of triisobutylaluminum (1M) and 0.17 g of a bis(phenylmethyl)bis(n-propylcyclopentadienyl)zirconium metallocene compound were mixed with 20 ml of toluene and injected into the reactor. After reacting at 60° C. for 2 hours, the supernatant was removed at room temperature and washed with toluene. After that, it was washed with normal hexane and then dried under reduced pressure to prepare a supported catalyst of free flowing powder.

<Ethylene Polymerization>

10 mg of the prepared solid supported catalyst was weighed in a glove box, and 1 liter of purified hexane and 1.0 ml of triisobutyl aluminum 1M nucleic acid dilution were injected into a stainless steel reactor with a volume of 2 liters equipped with a stirrer and a heating and cooling device. After that, they were introduced sequentially. Thereafter, the temperature of the reactor was raised to 80° C., and polymerization was performed for 1 hour by continuously introducing ethylene gas so that the pressure of the reactor was 350 psig. Thereafter, the gas supply was cut off and the pressure was removed to terminate the reaction. The polymer obtained therefrom was mostly removed by filtration of the polymerization solvent, and then dried in a vacuum oven at 70° C. to obtain a polyethylene polymer.

Example 2

It is the same as in Example 1 except that 1.35 g of Tri (pentafluorophenyl) borane was used instead of 0.4 g of Tri (pentafluorophenyl) borane.

Example 3

2.5 g of calcined silica (Grace Davison, SYLOPOL 2402) was weighed into a 1L reactor maintained in a nitrogen state, and 10 ml of toluene was added as a slurry, followed by stirring. After sufficiently dispersing the silica, 1.0 ml of n-BuLi (2.5M) was injected into the reactor. After reacting at 60 ° C. for 5 hours, the supernatant was removed at room temperature and then washed with toluene.

Thereafter, 0.4 g of Tri(pentafluorophenyl)borane dissolved in 20 ml of toluene was slowly injected into the reactor, followed by reaction at 60° C. for 5 hours. Thereafter, 0.22 g of trityl chloride was added at room temperature, stirred for an additional 12 hours, and the supernatant was removed at room temperature, followed by washing with toluene.

2.5 ml of triisobutylaluminum (1M) and 0.17 g of a bis(phenylmethyl)bis(n-propylcyclopentadienyl)zirconium metallocene compound were mixed with 20 ml of toluene and injected into the reactor. After reacting at 60° C. for 2 hours, the supernatant was removed at room temperature and washed with toluene. After that, it was washed with normal hexane and then dried under reduced pressure to prepare a supported catalyst of free flowing powder.

It is the same as Example 1 except that the supported catalyst prepared above was used.

Comparative Example 1

2.5 g of calcined silica (Grace Davison, SYLOPOL 2402) was weighed into a 1L reactor maintained in a nitrogen state, and 10 ml of toluene was added as a slurry, followed by stirring. Here, 23 ml of methylaluminoxane (10% by weight) was mixed with 0.17 g of a bis(phenylmethyl)bis(n-propylcyclopentadienyl)zirconium metallocene compound and injected into the reactor. After reacting at 60° C. for 2 hours, the supernatant was removed at room temperature and washed with toluene. After that, it was washed with normal hexane and then dried under reduced pressure to prepare a supported catalyst of free flowing powder.

It is the same as Example 1 except that the supported catalyst prepared above was used.

(A: Dimethylaniline, B: Tri(pentafluorophenyl)borane, T: Trityl chloride, TIBA: Triisobutylaluminum)

Claims (7)

A carrier made of any one of silica, silica-alumina or silica-magnesia;
(1) preparing a carrier to which a compound containing boron represented by Chemical Formula 1 or 2 is bonded by chemically bonding a compound containing boron to;
(2) supporting a cocatalyst containing aluminum on a carrier to which the compound containing boron is bonded; and
Step (3) of supporting one or more metallocene compounds represented by the following Chemical Formula 3 in step (2);
Method for producing a supported metallocene catalyst comprising a.
(However, the above steps (2) and (3) can be done at once or the order can be changed.)
[Formula 1]

[Formula 2]

(In Formulas 1 and 2 above,
B is a boron atom;
R is phenyl or phenyloxy, and phenyl or phenyloxy is 3 to 5 selected from fluorine atom, C1 to C20 alkyl optionally substituted by fluorine atom, or C1 to C20 alkoxy optionally substituted by fluorine atom. may be further substituted with substituents;
[L ^a ] ⁺ is a C5 to C7 cycloalkyl radical, a (C1 to C20)alkyl(C6 to C20)aryl radical, or a (C6 to C30)aryl(C1 to C20)alkyl radical;
[L ^b -H] ⁺ is an ammonium or phosphonium ion substituted with 1-3 (C1 to C20) alkyl groups).
[Formula 3]

(In Formula 3,
M is a Group 4 transition metal;
Cp ¹ and Cp ² are each independently a ligand having a cyclopentadienyl skeleton;
The ligand is an alkyl group having 1 to 20 carbon atoms, an alkylsilyl group, a silylalkyl group, a haloalkyl group, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. It may have 20 aryl groups, arylalkyl groups, alkylaryl groups, arylsilyl groups, silylaryl groups or halogen groups as substituents, and the substituents A ring can be formed by bonding between the liver;
X is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkylsilyl group, a silylalkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group group, an alkylaryl group, an arylsilyl group, a silylaryl group, an alkoxy group having 1 to 20 carbon atoms, an alkylsiloxy group, an aryloxy having 6 to 20 carbon atoms ( Aryloxy group, halogen group or amine group.) delete According to claim 1,
The cocatalyst comprising aluminum includes organoaluminum or an aluminoxane, wherein the organoaluminum is trimethylaluminum, triethylaluminium, triisobutylaluminum, trihexylaluminum, or trioctylaluminum, and the aluminoxane is linear and/or cyclic. It includes an alkylaluminoxane oligomer, and when the aluminoxane is a linear aluminoxane oligomer, it is represented by the formula R-(Al(R)-O)n-AlR ₂ , and when the aluminoxane is a cyclic aluminoxane oligomer, it is represented by the formula ( Represented by -Al(R)-O-)m, where R is a C1 to C8 alkyl group, n is 1 to 40, and m is 3 to 40. A method for preparing a supported metallocene catalyst. A supported metallocene catalyst prepared according to the method of claim 1 or 3. A method for producing a polyolefin, comprising the step of polymerizing an olefin monomer in the presence of the supported metallocene catalyst according to claim 4. According to claim 5,
A method for producing polyolefin, characterized in that the polymerization is carried out in a slurry process or gas phase process. According to claim 5,
The olefin monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, A method for producing a polyolefin comprising at least one selected from the group consisting of 1-tetradecene, 1-hexadecene, 1-itocene, dicyclopentadiene, and norbornadiene.